Dyes of the 2,4-dihydroxyquinoline series

ABSTRACT

New dyes having the formula:   IN WHICH R1 denotes a hydrogen atom, a halogen atom or a nitro group, n denotes the integer 1 or 2, R2 denotes a hydrogen atom, an unsubstituted or substituted alkyl group having one to three carbon atoms, an aromatic radical or, together with DENOTES A FIVE-MEMBERED OR SIX-MEMBERED CARBOCYCLIC OR HETEROCYCLIC RING WHICH MAY CONTAIN SUBSTITUENTS AND CONDENSED RINGS, AND R3 may also denote an unsubstituted or substituted alkyl group having one to three carbon atoms or an aliphatic, aromatic or heterocyclic radical which may be attached by way of -CO-. The dyes are pigment dyes.

United States Patent 11 1 Gaeng et al.

[ 1 Feb. 6, 1973 54 DYES OF THE 2,4-

DIHYDROXYQUINOLINE SERIES [75] Inventors: Manfred Gaeng, Bobenheim-Roxheim; Peter Dimroth, Ludwigshafen, both of Germany [73] Assignee: Badische Anilin- & Soda-Fabrik Aka ee lssh ft. Ludwigshafen/R- hine, Germany Feb. 25, 1970 Germany ..P 20 08 676.4

52 US. (:1 ..260/288 R, 106/22, 106/288 Q,

260/154, 260/155, 260/256.4 R, 260/289 R 51 t. (:1. ..C07d 33/50 [58] Field of Search ..260/288 R, 155

[56] References Cited UNITED STATES PATENTS 2,029,647 2/1936 Wizinger ..260/155 2,231,705 2/1941 Dickey .....260/l55 2,993,884 7/l961 Ruegg ..260/l55 Primary Examiner-Donald G. Daus Attorney-Johnston, Root, OKeeffe, Keil, Thompson & Shurtleff [5 7] ABSTRACT New dyes having the formula:

OH CH1 R2 I C=NN=O\ (R in which R denotes a hydrogen atom, a halogen atom or a nitro group, n denotes the integer 1 or 2, R denotes a hydrogen atom, an unsubstituted or substituted alkyl group having one to three carbon atoms, an aromatic radical or, together with denotes a five-membered or six-membered carbocyclic or heterocyclic ring which may contain substituents and condensed rings, and R may also denote an unsubstituted or substituted alkyl group having one to three carbon atoms or an aliphatic, aromatic or heterocyclic radical which may be attached by way of -CO.

The dyes are pigment dyes.

7 Claims, N0 Drawings DYES OF THE 2,4-DIHYDROXYQUINOLINE SERIES The invention relates to new dyes of the 2,4- dihydroxyquinoline series. The dyes have the formula:

in which R denotes a hydrogen atom, a halogen atom or a nitro group, n denotes the integer l or 2, R denotes a hydrogen atom, an unsubstituted or substituted alkyl group having one to three carbon atoms, an aromatic radical, or together with on (I) and organic solvents and because of their good fastness,

properties and high brilliance, they are outstandingly suitable as pigment dyes.

In the new dyes having the formula (I), the halogen atom denoted by R may be a chlorine or bromine atom. Examples of unsubstituted or substituted alkyl groups having one to three carbon atoms are:

Examples of aromatic radicals are aryl radicals such as phenyl or naphthyl radicals which may bear hydroxy groups, halogen atoms such as chlorine or bromine atoms, or methoxy groups as substituents. Examples of which the dyes having the formula (I) may contain are the members:

2 --c1 @an 0 01 01 N02 U- i M01 i u N Ofthe new dyes, those dyes having the formula (II):

in which R denotes a hydrogen, chlorine or bromine atom and n denotes the integer 1 or 2 are of particular industrial interest.

The new dyes may be prepared for example by reacting in an organic solvent a hydrazone having the formula (Ill):

OH (III) in which R an d n have the above meanings with a compound having the formula (IV):

in which R and R have the above meanings. Examples of suitable organic solvents are ethanol, n-propanol, isopropanol, n-butanol, isobutanol, glycol monomethyl ether, glycol monoethyl ether, glycol monobutyl ether, propylene glycol, propionic acid, ethylene glycol, glacial acetic acid or mixtures of these solvents. The reaction is preferably carried out within the temperature range from to 130 C.

According to a particularly advantageous embodiment of the manufacturing process, the dyes according to the invention may be obtained in a single vessel by first preparing the hydrazone having the formula (III) in the said solvents from the appropriate 3-acetyl- 2,4- dihydroxyquinoline and hydrazine hydrate at a temperature of from 40 to 70 C and then carrying out the reaction with the compound having the formula (IV) (without isolating the hydrazone) at a temperature of from 70 to 130 C, preferably from to C.

Examples of starting materials having the formula (III) are the hydrazones of 3-acetyl-2,4-dihydroxyquinoline, 6,8-dichloro-3-acetyl-2,4-dihydroxyquinoline and 6-nitro-3-acetyl-2,4-dihydroxyquinoline.

Examples of starting materials having the formula (IV) are ketones such as acetone or benzophenone; acetoacetic acid arylides such as the anilide, ochloroanilide or p-methoxyanilide of acetoacetic acid; a, B-diketones such as diacetyl, benzil, acenapthenequinone or phenanthrenequinone; unsubstituted or substituted isatins such as isatin, 5-chloroisatin, 5,7- dichlorolsatin, S-bromoisatin or 5-nitroisatin; aromatic EXAMPLE 1 21.7 parts of the hydrazone of 3-acetyl-2,4-dihydroxyquinoline and 12.2 parts of salicylaldehyde in 700 I parts of glacial acetic acid are boiled under reflux for 3 hours. The reaction mixture is then suction filtered at room temperature and the residue is washed with glacial acetic acid and water and dried. 27.4 parts ofa yellow pigment having the formula:

CH3 LHW OH Ki is obtained having a melting point of 325 C.

EXAMPLE 2 The 12.2 parts of salicylaldehyde in Example 1 is replaced by 17.2 parts of B-hydroxynaphthaldehyde. 37 parts ofa yellow pigment having the formula:

is obtained having a melting point of 349 C. The pigment exhibits a very good brilliance in coating compositions and has good color strength.

EXAMPLE 3 The 12.2 parts of salicylaldehyde in Example 1 is replaced by 20.2 parts of 1-phenyl-3methyl-5-hydroxypyrazolaldehyde-(4). 36 parts of a yellow pigment having the formula:

I C=N-N=CH CH;

1 N O I OH] N is obtained having a melting point of 305 to 307 C.

EXAMPLE 4 21.7 parts of the hydrazone of 3-acetyl-2,4-dihydroxyquinoline and 17.7 parts of acetoacetic anilide in 650 parts of glacial acetic acid are boiled under reflux for four hours. The reaction mixture is then suction filtered and the residue is washed with glacial acetic acid and water and dried. 15 parts of a greenish yellow pigment having the formula:

is obtained which in coating compositions has not only good color strength but also a very pure green yellow shade.

EXAMPLE 5 21.7 parts of the hydrazone of 3-acetyl-2,4-dihydroxyquinoline and 18.2 parts of benzophenone in 400 parts of glycol monomethyl ether are boiled for four hours under reflux. After suction filtration, washing and drying, 13 parts ofa yellow pigment having the formula:

I CH1 CeHs I7=NN=C Col-I5 OH is obtained.

EXAMPLE 6 21.7 parts of the hydrazone of 3-acetyl-2,4-dihydroxyquinoline and 21 parts of benzil in 500 parts of glacial acetic acid are boiled under reflux for 3 hours. After suction filtration, washing and drying, 15 parts of a greenish yellow pigment having the formula:

is obtained having a very pure shade both in coating compositions and in prints.

EXAMPLE 7 21.7 parts of the hydrazone of 3-acetyl-2,4-dihydroxyquinoline is reacted with 20.8 parts of phenanthrenequinone as described in Example 6.

20.2 parts of a red pigment is obtained having the formula:

EXAMPLE 8 and having a melting point of 338 C. In coating compositions the pigment exhibits a brilliant reddish yellow shade having remarkably high transparency and very good color strength.

EXAMPLE 9 20 parts ofthe pigment described in Example 8 is obtained by boiling 20.3 parts of 3-acetyl-2,4-dihydroxyquinoline with l6.l parts of isatin B-hydrazone and 8.5 parts of anhydrous sodium acetate in 400 parts of glacial acetic acid under reflux for 5 hours.

EXAMPLE 10 31.5 parts of the pigment described in Example 8 is obtained by boiling under reflux two hours 20.3 parts of 3-acetyl-2,4-dihydroxyquinoline with 5 parts of hydrazine hydrate in 200 parts of ethanol, then adding 14.7 parts of isatin and 200 parts of glacial acetic acid and heating the mixture under reflux for another three hours.

EXAMPLE ll and having a melting point of 347C.

EXAMPLE 12 The 21.7 partsof the hydrazone of 3-acetyl-2,4-

dihydroxyquinoline in Example 8 is replaced by 27.2 7

parts of the hydrazone of 6,8-dichloro-3-acetyl-2,4- dihydroxyquinoline. 28 parts of a red pigment is obtained having the formula:

and having a melting point of 240 C.

EXAMPLE 13 The 21.7 parts of the hydrazone of 3-acetyl-2,4-

dihydroxyquinoline in Example 8 is replaced by 26.2 parts of the hydrazone of 6-nitro-3-acetyl-2,4- dihydroxyquinoline. 31 parts of a red pigment is obtained having the formula:

EXAMPLE 14 27 parts of the pigment described in Example 13 is obtained by heating 24.8 parts of 6-nitro-3-acetyl-2,4- dihydroxyquinoline with 5 parts of hydrazine hydrate in 200 parts of ethanol for two hours at 60 to C, then adding 14,7 parts of isatin and 200 parts of glacial acetic acid and boiling under reflux for another three hours.

EXAMPLE 15 21.7 parts of the hydrazone of 3-acetyl-2,4-dihydroxyquinoline is heated under reflux for three hours with 5.8 parts of acetone in 300 parts of glycol monomethyl ether. The reaction mixture is suction filtered, and the residue is washed and dried. 23 parts of a yellow pigment is obtained having the formula:

5 parts of the pigment obtained according to Example 8, 9 or 10 is ground in an attrition mill with parts of acrylic resin coating composition (consisting of 80 parts of acrylic resin solution and 20 parts of melamine resin solution). An orange-colored coating composition having good color strength is obtained which after having been baked for 30 minutes at C exhibits very good fastness to light and overspraying.

By diluting 2 parts of the said acrylic resin varnish with 20 parts of a white coating composition (consisting of 20 parts of titanium dioxide and 80 parts of acrylic resin coating composition), a reddish yellow coating composition having good depth of color is obtained which exhibits good fastness to light and overspraying after baking.

20 parts of the pigment obtained according to Example l is ground with 80 parts of book-printing or offset varnish in the conventional way on a three roll mill.

The printing ink prepared in this way gives prints having excellent color strength, light fastness and brilliance when processed in book printing and offset printing. Printing inks having similar properties are obtained 'when pigments described in the other Examples are used.

We claim: 1. A dye having the formula 4. A dye having the formula in which R denotes hydrogen, halogen or nitro, n denotes the integer l or 2, R denotes hydrogen or 1) cm I together with @TJ [D l :2 i o 1 o I l the radical ofthe formula 5. A dye having the formula i on;

U:( =N-N -01 o (R )m N/ OW H le 1'1 H l I 6. A dye having the formula wherein R denotes chlorine, bromine or mtro with m being the integer l or 2, and R denotes 2-hydroxy OH phenyl or 2-hydroxy-naphthyl-(l) when R is hydrogen. Cl J=N-N 2.Adye having the formula \N OH O N/ E 7. A dye having the formula l t CH OH 0 a OH H N 0 wherein R denotes hydrogen, chlorine or bromine and m denotes the integer l or 2.

3.Adyehavingtheformula l 

1. A dye having the formula
 2. A dye having the formula
 3. A dye having the formula
 4. A dye having the formula
 5. A dye having the formula
 6. A dye having the formula 